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1.
Int J Surg ; 2024 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-38833338

RESUMO

BACKGROUND: The demand for telesurgery is rapidly increasing. Augmented reality (AR) remote surgery is a promising alternative, fulfilling a worldwide need in fracture surgery. However, previous AR endoscopic and Google Glass remotes remain unsuitable for fracture surgery, and the application of remote fracture surgery has not been reported. We aimed to evaluated the safety and clinical effectiveness of a new AR remote in fracture surgery. MATERIALS AND METHODS: This retrospective non-inferiority cohort study was conducted at three centres. Between January 1, 2018, and March 31, 2022, 800 patients who underwent fracture surgery were eligible for participation. The study enrolled 551 patients with fractures (132 patellae, 128 elbows, 126 tibial plateaus, and 165 ankles) divided into an AR group (specialists used AR to remotely guide junior doctors to perform surgeries) and a traditional non-remote group (specialists performed the surgery themselves). RESULTS: Among 364 patients (182 per group) matched by propensity score, seven (3.8%) in the AR group and four (3%) in the non-remote group developed complications. The 0.005 risk difference (95% confidence interval: -0.033 to 0.044) was below the pre-defined non-inferiority margin of a 10% absolute increase. A similar distribution in the individual components of all complications was found between the groups. Hierarchical analysis following propensity score matching revealed no statistical difference between the two groups regarding functional results at 1-year follow-up, operative time, amount of bleeding, number of fluoroscopies, and injury surgery interval. A Likert scale questionnaire showed positive results (median scores: 4-5) for safety, efficiency, and education. CONCLUSION: This study is the first to report that AR remote surgery can be as safe and effective as that performed by a specialist in person for fracture surgery, even without the physical presence of a specialist, and is associated with improving the skills and increasing the confidence of junior surgeons. This technique is promising for remote fracture surgery and other open surgeries, offering a new strategy to address inadequate medical care in remote areas.

2.
Am J Sports Med ; : 3635465241254524, 2024 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-38884318

RESUMO

BACKGROUND: Use of a rapid rehabilitation protocol for postoperative recovery after recurrent patellar dislocation (RPD) has gradually gained attention; nonetheless, evidence of its safety and effectiveness is lacking. PURPOSE: To compare the short-term postoperative outcomes of early rapid rehabilitation with those of conservative rehabilitation in patients with RPD. STUDY DESIGN: Randomized controlled trial; Level of evidence, 2. METHODS: A total of 50 patients with RPD who underwent tibial tubercle osteotomy combined with medial patellofemoral ligament reconstruction were enrolled between January 2018 and February 2019. Postoperatively, the patients were randomly assigned to either the early rapid group (rapid group; n = 25 patients) or the conservative group (control group; n = 25 patients) for rehabilitation training. The rapid group underwent faster progression in weightbearing and range of motion (ROM) training. Knee joint functional scores, ROM, bilateral thigh circumference differences, and imaging data were recorded preoperatively and at 6 weeks and 3, 6, 12, and 24 months postoperatively for comparison. Postoperative complications were recorded over the 24-month follow-up period. RESULTS: The baseline data did not significantly differ between the 2 groups. Postoperatively, compared with the control group, the rapid group had higher Tegner scores at 6 weeks and 3 months; higher Lysholm scores at 3 and 6 months; higher International Knee Documentation Committee scores at 6 weeks, 3 months, and 12 months; better ROM; and smaller bilateral thigh circumference differences at 24 months (P < .05 for all). However, no differences were observed in the Tegner, Lysholm, and International Knee Documentation Committee scores at 24 months postoperatively. At the 6-week and subsequent follow-up visits, the Caton and Insall indices were lower in the control group than in the rapid group (P < .01 for all). Moreover, compared with the control group, the rapid group had a lower incidence of patella baja at 24 months (0% vs 17%) and fewer complications during the whole follow-up period (P < .01). CONCLUSION: Early rapid postoperative rehabilitation appears to be safe and effective for patients who undergo tibial tubercle osteotomy combined with medial patellofemoral ligament reconstruction to treat RPD. In the short term, this approach was shown to be more advantageous than conservative rehabilitation in improving functional scores, allowing an earlier return to daily activities, although the lack of difference at 24 months implies no long-term benefits. In addition, it potentially helped to prevent the occurrence of complications, including patella baja. REGISTRATION: ChiCTR1800014648 (ClinicalTrials.gov identifier).

3.
Discov Oncol ; 15(1): 143, 2024 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-38704809

RESUMO

PURPOSE: Pancreatic cancer (PC) is one of the most lethal malignant gastrointestinal tumors (GI) characterized by a poor prognosis. Ferroptosis is an emerging programmed cell death that plays an essential role in the progression of various cancers. Ferroptosis is driven by iron-dependent phospholipid peroxidation and is regulated by mitochondrial activity, lipid peroxidation, and reactive oxygen species (ROS). The function and mechanism of ferroptosis in PC need more research. METHODS: The levels of circRNAs, miRNAs, and mRNAs were detected by quantitative real-time polymerase chain reaction (qRT-PCR). Western blot was used for protein detection. CCK8 assays were used to detect cell proliferation. Cell death, lipid peroxidation, ROS, and Fe2+ were detected by indicted kits. Dual-luciferase reporter and RNA pull-down assays were conducted to confirm the interaction between circRNAs, miRNAs, and mRNAs. RESULTS: In this research, we found that circular RNA hsa_circ_0000003(circ_WASF2) was upregulated in pancreatic cancer cells. The silence of circ_WASF2 inhibited cancer proliferation and increased cell death by increasing ferroptosis accompanied by up-regulation of lipid peroxidation, ROS, and Fe2+. Further studies showed that circ_WASF2 could attenuate ferroptosis by targeting miR-634 and the downstream glutathione peroxidase 4 (GPX4). GPX4 has been well-reported as a central factor in ferroptosis. Our research revealed a new pathway for regulating ferroptosis in PC. CONCLUSION: In summary, we have determined that circ_WASF2/miR-634/GPX4 contributed to ferroptosis-induced cell death, and provided a possible therapeutic target in PC.

5.
Orthop J Sports Med ; 12(2): 23259671241226719, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38343645

RESUMO

Background: Limited literature is available regarding the effect of subchondral cysts on the surgical outcomes for treatment of osteochondral lesion of the talus (OLT). Purpose: To conduct a systematic review and meta-analysis of studies comparing surgical outcomes between OLTs with and without cysts. Study Design: Systematic review; Level of evidence, 4. Methods: Following the PRISMA (Preferred Reporting Items for Systematic Reviews and Meta-Analyses) guidelines, the authors searched PubMed, Embase, Web of Science, and the Cochrane Library for relevant studies published up to January 7, 2023. The 4375 retrieved studies were screened, and 9 articles (level of evidence, 2-4) were included, which comprised 165 patients with OLT and subchondral cysts (cyst group) and 223 without cysts (noncyst group). After data extraction, mean differences in outcome scores (American Orthopaedic Foot and Ankle Society [AOFAS] Ankle Hindfoot Scale, visual analog scale [VAS] score for pain) and adverse events were compared between the groups. Results: Functional scores improved after surgery in both groups, with the cyst group having a significantly higher AOFAS score than the noncyst group (P = .005; I2 = 0%); subgroup analysis revealed that this difference was attributable to the size of the osteochondral lesion and the type of surgical procedure. No significant difference was found between the cyst and noncyst groups in VAS pain scores (P = .77; I2 = 0%) or postoperative adverse events (P = .35; I2 = 0%). Conclusion: The results of this review indicated that patients with subchondral cysts improved with surgical treatment of OLT. A relatively low level of evidence was available to indicate that surgical treatment for small OLTs with subchondral cysts will result in better clinical outcomes compared with OLTs without cysts.

6.
Medicine (Baltimore) ; 103(2): e36926, 2024 Jan 12.
Artigo em Inglês | MEDLINE | ID: mdl-38215088

RESUMO

RATIONALE: Primary hepatic mucosa-associated lymphoid tissue (MALT) lymphoma is a rare malignant primary hepatic lymphoma. The sensible choice of treatment for patients with primary lymphoma combined with atrial fibrillation (AF) is controversial and challenging. PATIENT CONCERNS: The patient presented with both primary hepatic MALT lymphoma and AF, which was difficult to manage. DIAGNOSES: Pathological and immunohistochemical examination are helpful for definitive diagnosis. INTERVENTIONS: Surgical resection and subsequent anticoagulant therapy are main treatment methods, and adjuvant therapy depends on the situation. OUTCOMES: Primary hepatic MALT lymphoma is easy to misdiagnosis due to a lack of typical symptoms and imaging signs. LESSONS: This case highlights for patients with primary hepatic MALT lymphoma combined with AF, toxicity caused by adjuvant chemotherapy should be fully considered, and careful selection should be made based on the general conditions and complications of patients.


Assuntos
Fibrilação Atrial , Linfoma de Zona Marginal Tipo Células B , Humanos , Linfoma de Zona Marginal Tipo Células B/complicações , Linfoma de Zona Marginal Tipo Células B/diagnóstico , Linfoma de Zona Marginal Tipo Células B/tratamento farmacológico , Fibrilação Atrial/complicações
7.
Environ Sci Ecotechnol ; 20: 100375, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38283869

RESUMO

Bioelectrochemical systems (BES) have emerged as a dual-function technology for treating wastewater and recovering energy. A vital element of BES is the rapid formation and maintenance of electroactive biofilms (EABs). Previous attempts to accelerate EAB formation and improve electroactivities focused on enhancing the bacterial adhesion process while neglecting the rate-limiting step of the bacterial transport process. Here, we introduce membrane filtration into BES, establishing a dynamic membrane filtration system that enhances overall performance. We observed that optimal membrane flux considerably reduced the startup time for EAB formation. Specifically, EABs established under a 25 L m-2 h-1 flux (EAB25 LMH) had a formation time of 43.8 ± 1.3 h, notably faster than the 51.4 ± 1.6 h in the static state (EAB0 LMH). Additionally, EAB25 LMH exhibited a significant increase in maximum current density, approximately 2.2 times higher than EAB0 LMH. Pearson correlation analysis indicated a positive relationship between current densities and biomass quantities and an inverse correlation with startup time. Microbial analysis revealed two critical findings: (i) variations in maximum current densities across different filtration conditions were associated with redox-active substances and biomass accumulation, and (ii) the incorporation of a filtration process in EAB formation enhanced the proportion of viable cells and encouraged a more diverse range of electroactive bacteria. Moreover, the novel electroactive membrane demonstrated sustained current production and effective solid-liquid separation during prolonged operation, indicating its potential as a viable alternative in membrane-based systems. This approach not only provides a new operational model for BES but also holds promise for expanding its application in future wastewater treatment solutions.

9.
Inorg Chem ; 62(48): 19603-19611, 2023 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-37971601

RESUMO

The first two discrete, fully inorganic platinum(II/IV)-arsenito clusters, [fac-PtIV(As3O6)2]2- (PtAs6) and [Pt4II(H2AsO3)6(HAsO3)2]2- (Pt4As8), as well as the platinum(II)-arsenito heteropolytungstate [Pt2IIAs6W4O28]10- (Pt2As6W4), have been synthesized in aqueous media using simple one-pot reaction conditions. In PtAs6, a PtIV ion is coordinated to two cyclic, tridentate As3O6 units via oxo-donation (PtIV-O ∼ 2.02 Å). In Pt4As8, each PtII ion is coordinated to four AsO3 ligands via two oxygens and two AsIII atoms in a square-planar fashion (PtII-AsIII 2.31 Å, PtII-O 2.07 Å), resulting in an open cage-like structure, which forms a strong tetrameric assembly in the solid state mediated by two K+ counterions. In Pt2As6W4, each PtII ion is coordinated by the As atoms of three AsO3 ligands (PtII-AsIII 2.38 Å) and an oxo group (PtII-O 2.07 Å) in addition to bridging two tungsten ions, and this polyanion was characterized in solution by 195Pt NMR.

10.
J Formos Med Assoc ; 2023 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-37996320

RESUMO

BACKGROUND/PURPOSE: Autonomic nervous system (ANS) disorders may occur in skeletal muscle disease, but the link between them has not been fully established. Studying the relationship between them may yield insights into the mechanisms and treatment of disease. This study aimed to explore the association between heart rate variability (HRV), sarcopenia, and subscales of sarcopenia (muscle mass, muscle strength, and physical mobility). METHODS: 2514 community-dwelling older Chinese participants were included in this study. The Asian Working Group for Sarcopenia guidelines were used to define sarcopenia. HRV was measured by 90-s electrocardiogram RR interval data. All HRV parameters were transformed using natural logarithms. Multiple regression analysis and multivariate linear regression was performed using potential correlates. RESULTS: The overall prevalence of sarcopenia was 15.1 % (18.5 % in males and 12.6 % in females). In the logistic regression analysis model, there was a significant association between log-transformed standard deviation of RR interval (lnSDNN) (OR = 0.736, p = 0.019), log-transformed coefficient of variation of RR intervals (lnCVRR) (OR = 0.751, p = 0.020), log-transformed low-frequency power (lnLF) (OR = 0.861, p = 0.008), log-transformed high-frequency power (lnHF) (OR = 0.864, p = 0.003) and sarcopenia in the general population after adjusting for age, sex, body mass index (BMI), daily activity levels, hypertension, heart disease and cardiac drugs. In addition, in multivariate linear regression, lnSDNN (ß = 0.146, p = 0.001), lnCVRR (ß = 0.120, p = 0.010), lnLF (ß = 0.066, p = 0.002) and lnHF (ß = 0.065, p < 0.001) remained significantly positively associated with muscle mass, but there were no significant differences in grip strength and walking speed. CONCLUSIONS: Sarcopenia was independently associated with lower heart rate variability in a community-dwelling elderly Chinese population. In addition, muscle mass was positively associated with heart rate variability in the elderly.

12.
Curr Med Chem ; 2023 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-37859412

RESUMO

High concentrations of reactive oxygen species (ROS) can disrupt cell structure and induce apoptosis and necrosis of tumor cells. Photodynamic therapy (PDT) and chemodynamic therapy (CDT) are two cancer treatments mediated by reactive oxygen species. Oxygen molecules (O2 ) are one of the indispensable factors in PDT and hypoxic tumor sites limit its application. However, another ROS-mediated method, CDT, can generate •OH and O2 in situ by Fenton reaction or Fenton-like reaction. Synergistic PDT/CDT therapy is a strategy to overcome the limitations of tumor microenvironment therapy. In this review, PDT and CDT therapies are briefly introduced, with an emphasis on metal-basrd porphyrin nanoparticles constructed in different ways for PDT/CDT dual-mode therapy. By introducing the history and latest design schemes of the treatment model, it provides ideas for researchers engaged in ROS-mediated cancer therapies.

13.
J Foot Ankle Res ; 16(1): 57, 2023 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-37674248

RESUMO

BACKGROUND: Surgical resection of Morton's neuroma includes dorsal and plantar approaches. However, there is no consensus on the choice of approach in clinic. The purpose of this study was to conduct a systematic review and meta-analysis to compare the surgical results of dorsal and plantar approaches. METHODS: The literatures of PubMed, Cochrane library, Embase and Web of Science were searched on April 26th, 2023. A systematic review was performed using the Preferred Reporting Items for Systematic Reviews and Meta-Analysis guidelines. The data were extracted after screening the literature and evaluating the quality of the methodology included in the study. The RevMan5.4 software was used to analyze and calculate the OR value and 95% confidence interval. RESULTS: A total of 7 randomized controlled trials and comparative studies were published, of which only 5 were included. There were 158 feet via plantar approach (plantar group, PG) and 189 via dorsal approach (dorsal group, DG). There was no significant difference between PG and DG in overall adverse events, sensory problems, incision infection and deep vein thrombosis (p > 0.05). In terms of scar problems, PG showed more than DG (OR, 2.90[95%CI, 1.40 to 5.98]; p = 0.004). Other outcome indicators such as visual analogue scale (VAS) scores and American Orthopedic Foot and Ankle Society (AOFAS) scores were difficult to be included in the comparison. CONCLUSIONS: Based on the relatively low quality and small amount of available evidence, the meta-analysis conducted produces a hypothesis that the frequency of adverse events in surgical treatment of Morton's neuroma, dorsal approach and plantar approach may be the same, but the types are different. More high-level evidence is needed to further verify this hypothesis.


Assuntos
Neuroma Intermetatársico , Ortopedia , Humanos , Neuroma Intermetatársico/cirurgia , Consenso , Extremidade Inferior , Software
14.
Front Med (Lausanne) ; 10: 1224489, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37663656

RESUMO

Objectives: To explore an intelligent detection technology based on deep learning algorithms to assist the clinical diagnosis of distal radius fractures (DRFs), and further compare it with human performance to verify the feasibility of this method. Methods: A total of 3,240 patients (fracture: n = 1,620, normal: n = 1,620) were included in this study, with a total of 3,276 wrist joint anteroposterior (AP) X-ray films (1,639 fractured, 1,637 normal) and 3,260 wrist joint lateral X-ray films (1,623 fractured, 1,637 normal). We divided the patients into training set, validation set and test set in a ratio of 7:1.5:1.5. The deep learning models were developed using the data from the training and validation sets, and then their effectiveness were evaluated using the data from the test set. Evaluate the diagnostic performance of deep learning models using receiver operating characteristic (ROC) curves and area under the curve (AUC), accuracy, sensitivity, and specificity, and compare them with medical professionals. Results: The deep learning ensemble model had excellent accuracy (97.03%), sensitivity (95.70%), and specificity (98.37%) in detecting DRFs. Among them, the accuracy of the AP view was 97.75%, the sensitivity 97.13%, and the specificity 98.37%; the accuracy of the lateral view was 96.32%, the sensitivity 94.26%, and the specificity 98.37%. When the wrist joint is counted, the accuracy was 97.55%, the sensitivity 98.36%, and the specificity 96.73%. In terms of these variables, the performance of the ensemble model is superior to that of both the orthopedic attending physician group and the radiology attending physician group. Conclusion: This deep learning ensemble model has excellent performance in detecting DRFs on plain X-ray films. Using this artificial intelligence model as a second expert to assist clinical diagnosis is expected to improve the accuracy of diagnosing DRFs and enhance clinical work efficiency.

15.
Front Bioeng Biotechnol ; 11: 1194009, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37539438

RESUMO

Objective: Explore a new deep learning (DL) object detection algorithm for clinical auxiliary diagnosis of lumbar spondylolisthesis and compare it with doctors' evaluation to verify the effectiveness and feasibility of the DL algorithm in the diagnosis of lumbar spondylolisthesis. Methods: Lumbar lateral radiographs of 1,596 patients with lumbar spondylolisthesis from three medical institutions were collected, and senior orthopedic surgeons and radiologists jointly diagnosed and marked them to establish a database. These radiographs were randomly divided into a training set (n = 1,117), a validation set (n = 240), and a test set (n = 239) in a ratio of 0.7 : 0.15: 0.15. We trained two DL models for automatic detection of spondylolisthesis and evaluated their diagnostic performance by PR curves, areas under the curve, precision, recall, F1-score. Then we chose the model with better performance and compared its results with professionals' evaluation. Results: A total of 1,780 annotations were marked for training (1,242), validation (263), and test (275). The Faster Region-based Convolutional Neural Network (R-CNN) showed better precision (0.935), recall (0.935), and F1-score (0.935) in the detection of spondylolisthesis, which outperformed the doctor group with precision (0.927), recall (0.892), f1-score (0.910). In addition, with the assistance of the DL model, the precision of the doctor group increased by 4.8%, the recall by 8.2%, the F1-score by 6.4%, and the average diagnosis time per plain X-ray was shortened by 7.139 s. Conclusion: The DL detection algorithm is an effective method for clinical diagnosis of lumbar spondylolisthesis. It can be used as an assistant expert to improve the accuracy of lumbar spondylolisthesis diagnosis and reduce the clinical workloads.

16.
Inorg Chem ; 62(33): 13195-13204, 2023 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-37555777

RESUMO

Three gallium(III)- and thallium(III)-containing polyoxopalladates (POPs) have been synthesized and structurally characterized in the solid state and in solution, namely, the phosphate-capped 12-palladate nanocubes [XPd12O8(PO4)8]13- (X = GaIII, GaPd12P8; X = TlIII, TlPd12P8) and the 23-palladate double-cube [Tl2IIIPd23P14O70(OH)2]20- (Tl2Pd23P14). The cuboid POPs, GaPd12P8 and TlPd12P8, are solution stable as verified by the respective 31P, 71Ga, and 205Tl nuclear magnetic resonance (NMR) spectra. Of prime interest, the spin-spin coupling schemes allowed for an intimate study of the solution behavior of the TlIII-containing POPs via a combination of 31P and 205Tl NMR, including the stoichiometry of the major fragments of Tl2Pd23P14. Moreover, biological studies demonstrated the antitumor and antiviral activity of GaPd12P8 and TlPd12P8, which were validated to be as efficient as cis-platinum against human melanoma and acute promyelocytic leukemia cells. Furthermore, GaPd12P8 and TlPd12P8 exerted inhibitory activity against two herpetic viruses, HSV-2 and HCMV, in a dose-response manner.


Assuntos
Gálio , Tálio , Humanos , Tálio/química , Gálio/farmacologia , Gálio/química , Ressonância Magnética Nuclear Biomolecular , Espectroscopia de Ressonância Magnética , Imageamento por Ressonância Magnética
17.
Inorg Chem ; 62(33): 13184-13194, 2023 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-37440284

RESUMO

The first PtIV-containing discrete polyoxoplatinate(II) [PtIVPtII6O6(AsO2(CH3)2)6]2- (Pt7) and polyoxopalladate(II) [PtIVPdII6O6(AsO2(CH3)2)6]2- (PtPd6) have been prepared and characterized in the solid state, in solution, and in the gas phase. The molecular structures of the noble metal-oxo clusters Pt7 and PtPd6 comprise a central, octahedral PtIVO6 hetero group surrounded by six square-planar MO4 (M = PtII, PdII) units, which are capped by six dimethylarsinate ligands. The polyanions were prepared under simple one-pot aqueous solution conditions by reacting H2Pt(OH)6 with either K2PtCl4 or Pd(NO3)2 in sodium dimethylarsinate buffer (pH 7) at 80 °C. Catalytic studies were performed on Pt7 supported on SBA15-apts for o-xylene hydrogenation at 300 °C and 90 bar H2 pressure and indicated excellent activity and recyclability with low activation temperature.

18.
BMC Bioinformatics ; 24(1): 264, 2023 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-37355560

RESUMO

A nonhomogeneous dynamic Bayesian network model, which combines the dynamic Bayesian network and the multi-change point process, solves the limitations of the dynamic Bayesian network in modeling non-stationary gene expression data to a certain extent. However, certain problems persist, such as the low network reconstruction accuracy and poor model convergence. Therefore, we propose an MD-birth move based on the Manhattan distance of the data points to increase the rationality of the multi-change point process. The underlying concept of the MD-birth move is that the direction of movement of the change point is assumed to have a larger Manhattan distance between the variance and the mean of its left and right data points. Considering the data instability characteristics, we propose a Markov chain Monte Carlo sampling method based on node-dependent particle filtering in addition to the multi-change point process. The candidate parent nodes to be sampled, which are close to the real state, are pushed to the high probability area through the particle filter, and the candidate parent node set to be sampled that is far from the real state is pushed to the low probability area and then sampled. In terms of reconstructing the gene regulatory network, the model proposed in this paper (FC-DBN) has better network reconstruction accuracy and model convergence speed than other corresponding models on the Saccharomyces cerevisiae data and RAF data.


Assuntos
Algoritmos , Redes Reguladoras de Genes , Teorema de Bayes , Cadeias de Markov , Saccharomyces cerevisiae/genética , Método de Monte Carlo
19.
Chem Commun (Camb) ; 59(39): 5918-5921, 2023 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-37171021

RESUMO

The first discrete mixed platinum(IV)-gold(III) oxoanion [PtIV2AuIII3O6((CH3)2AsO2)6]- (1) was synthesized by reaction of H2Pt(OH)6 with H[AuCl4] in a simple one-pot procedure in aqueous solution at pH 7 and comprises two equivalent PtIVO6(As(CH3)2)3 units which are linked by three square-planar AuIIIO4 units. Polyanion 1 could be isolated as a potassium or sodium salt in good yield, which were structurally characterized in the solid state by single-crystal XRD and TGA, and in solution by multinuclear (1H, 13C, 195Pt) NMR, indicating that polyanion 1 is stable in solution, which was confirmed by ESI-MS studies. The sodium salt of 1 undergoes a clean single-crystal-to-single-crystal (SCSC) structural transformation upon rehydration and dehydration.

20.
Molecules ; 28(8)2023 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-37110520

RESUMO

Endogenous and exogenous estrogens are widely present in food and food packaging, and high levels of natural estrogens and the misuse or illegal use of synthetic estrogens can lead to endocrine disorders and even cancer in humans. Therefore, it is consequently important to accurately evaluate the presence of food-functional ingredients or toxins with estrogen-like effects. In this study, an electrochemical sensor based on G protein-coupled estrogen receptors (GPERs) was fabricated by self-assembly, modified by double-layered gold nanoparticles, and used to measure the sensing kinetics for five GPER ligands. The interconnected allosteric constants (Ka) of the sensor for 17ß-estradiol, resveratrol, G-1, G-15, and bisphenol A were 8.90 × 10-17, 8.35 × 10-16, 8.00 × 10-15, 5.01 × 10-15, and 6.65 × 10-16 mol/L, respectively. The sensitivity of the sensor for the five ligands followed the order of 17ß-estradiol > bisphenol A > resveratrol > G-15 > G-1. The receptor sensor also demonstrated higher sensor sensitivity for natural estrogens than exogenous estrogens. The results of molecular simulation docking showed that the residues Arg, Glu, His, and Asn of GPER mainly formed hydrogen bonds with -OH, C-O-C, or -NH-. In this study, simulating the intracellular receptor signaling cascade with an electrochemical signal amplification system enabled us to directly measure GPER-ligand interactions and explore the kinetics after the self-assembly of GPERs on a biosensor. This study also provides a novel platform for the accurate functional evaluation of food-functional components and toxins.


Assuntos
Estrogênios , Nanopartículas Metálicas , Humanos , Receptores de Estrogênio/metabolismo , Resveratrol , Cinética , Ligantes , Ouro , Receptores Acoplados a Proteínas G/metabolismo , Estradiol , Proteínas de Ligação ao GTP
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